SUMMARY OF THE INVENTION
Subject matter of the invention constitutes surface-modified, pyrogenically produced mixed oxides which contain two or more components of the series SiO.sub.2, Al.sub.2 O.sub.3, TiO.sub.2, ZrO.sub.2, Fe.sub.2 O.sub.3, Nb.sub.2 O.sub.5, V.sub.2 O.sub.5, WO.sub.3, SnO.sub.2, GeO.sub.2 and were surface-modified with one or several compounds of the following groups:
(a) Organosilanes of the type (RO).sub.3 Si(C.sub.n H.sub.2n+1)
R=alkyl, such as e.g. methyl-, ethyl-, n-propyl-, i-propyl-, butyl-- PA1 n=1-20 PA1 R=alkyl, such as e.g. methyl-, ethyl-, n-propyl-, i-propyl-, butyl-- PA1 R=alkyl such as e.g. methyl-, ethyl-, n-propyl-, i-propyl-, butyl-- PA1 n=1-20 PA1 x=y=3 PA1 x=1, 2 PA1 y=1, 2 PA1 X=Cl, Br PA1 n=1-20 PA1 X=Cl, Br PA1 R'=alkyl, such as e.g. methyl-, ethyl-, n-propyl-, i-propyl-, butyl-- PA1 n=1-20 PA1 X=Cl, Br PA1 R'=alkyl, such as e.g. methyl-, ethyl-, n-propyl-, i-propyl-, butyl-- PA1 n=1-20 PA1 R=alkyl, such as methyl-, ethyl-, propyl-- PA1 m=0, 1-20 PA1 R'=methyl-, aryl (e.g. --C.sub.6 H.sub.5, substituted phenyl groups) PA1 --C.sub.4 F.sub.9, OCF.sub.2 --CHF--CF.sub.3, --C.sub.6 F.sub.13, --O--CF.sub.2 --CHF.sub.2 PA1 --NH.sub.2, --N.sub.3, --SCN, --CH.dbd.CH.sub.2, PA1 --OOC(CH.sub.3)C.dbd.CH.sub.2 PA1 --OCH.sub.2 --CH(O)CH.sub.2 ##STR2## --NH--COO--CH.sub.3, --NH--COO--CH.sub.2 --CH.sub.3, --NH--(CH.sub.2).sub.3 Si(OR).sub.3 PA1 --S.sub.x --(CH.sub.2).sub.3 Si(OR).sub.3 PA1 --NH.sub.2, --N.sub.3, --SCN, --CH.dbd.CH.sub.2, PA1 --OOC(CH.sub.3)C.dbd.CH.sub.2 PA1 --OCH.sub.2 --CH(O)CH.sub.2 ##STR3## --NH--COO--CH.sub.3, --NH--COO--CH.sub.2 --CH.sub.3, --NH--(CH.sub.2).sub.3 Si(OR).sub.3 PA1 --S.sub.x --(CH.sub.2).sub.3 Si(OR).sub.3 PA1 X=Cl, Br PA1 m=0, 1-20 PA1 R'=methyl-, aryl (e.g. --C.sub.6 H.sub.5, substituted phenyl groups) PA1 --C.sub.4 F.sub.9 OCF.sub.2 --CHF--CF.sub.3, --C.sub.6 F.sub.13, --O--CF.sub.2 --CHF.sub.2 PA1 --NH.sub.2, --N.sub.3, --SCN, --CH.dbd.CH.sub.2, PA1 --OOC(CH.sub.3)C.dbd.CH.sub.2 PA1 --OCH.sub.2 --CH(O)CH.sub.2 ##STR4## --NH--COO--CH.sub.3, --NH--COO--CH.sub.2 --CH.sub.3, --NH--(CH.sub.2).sub.3 Si(OR).sub.3 PA1 --S.sub.x --(CH.sub.2).sub.3 Si(OR).sub.3 PA1 X=Cl, Br PA1 R=alkyl, such as methyl-, ethyl-, propyl-- PA1 m=0, 1-20 PA1 R'=methyl-, aryl (e.g. --C.sub.6 H.sub.5, substituted phenyl groups) PA1 --C.sub.4 F.sub.9, OCF.sub.2 --CHF--CF.sub.3, --C.sub.6 F.sub.13, --O--CF.sub.2 --CHF.sub.2 PA1 --NH.sub.2, --N.sub.3, --SCN, --CH.dbd.CH.sub.2, PA1 --OOC(CH.sub.3)C.dbd.CH.sub.2 PA1 --OCH.sub.2 --CH(O)CH.sub.2 ##STR5## --NH--COO--CH.sub.3, --NH--COO--CH.sub.2 --CH.sub.3, --NH--(CH.sub.2).sub.3 Si(OR).sub.3, PA1 --S.sub.x --(CH.sub.2).sub.3 Si(OR).sub.3 PA1 X=Cl, Br PA1 R=alkyl PA1 m=0, 1-20 PA1 R'=methyl-, aryl (e.g. --C.sub.6 H.sub.5, substituted phenyl groups) PA1 --C.sub.4 F.sub.9, OCF.sub.2 --CHF--CF.sub.3, --C.sub.6 F.sub.13, --O--CF.sub.2 --CHF.sub.2 PA1 --NH.sub.2, --N.sub.3, --SCN, --CH.dbd.CH.sub.2, PA1 --OOC(CH.sub.3)C.dbd.CH.sub.2 PA1 --OCH.sub.2 --CH(O)CH.sub.2 ##STR6## --NH--COO--CH.sub.3, --NH--COO--CH.sub.2 --CH.sub.3, --NH--(CH.sub.2).sub.3 Si(OR).sub.3 PA1 --S.sub.x --(CH.sub.2).sub.3 Si(OR).sub.3 PA1 R'=alkyl such as C.sub.n H.sub.2n+1 in which n=1 to 20, aryl such as phenyl- and substituted phenyl groups, (CH.sub.2).sub.n --NH.sub.2, H PA1 R"=alkyl such as C.sub.n H.sub.2n+1 in which n=1 to 20, aryl such as phenyl- and substituted phenyl groups, (CH.sub.2).sub.n --NH.sub.2, H PA1 R'"=alkyl such as C.sub.n H.sub.2n+1 in which n=1 to 20, aryl such as phenyl- and substituted phenyl groups, (CH.sub.2).sub.n --NH.sub.2, H PA1 Reinforcement filler in silicone rubber and gum, PA1 Charge stabilizer and flow aid in toner powder, PA1 Free-flow agent, PA1 Anti-blocking aid, e.g. in foils, PA1 UV blocker, e.g. in cosmetics, PA1 Thickening agent, e.g. in paints.
(b) Organosilanes of the type R'.sub.x (RO).sub.y Si(C.sub.n H.sub.2n+1)
(c) Halogenorganosilanes of the type X.sub.3 Si(C.sub.n H.sub.2n+1)
(d) Halogenorganosilanes of the type X.sub.2 (R')Si(C.sub.n H.sub.2n+1)
(e) Halogenorganosilanes of the type X(R').sub.2 Si(C.sub.n H.sub.2n+1)
(f) Organosilanes of the type (RO).sub.3 Si(CH.sub.2).sub.m --R'
(g) Organosilanes of the type (R").sub.x (RO).sub.y Si(CH.sub.2).sub.m --R' ##EQU1## R'=methyl-, aryl (e.g. --C.sub.6 H.sub.5, substituted phenyl groups) --C.sub.4 F.sub.9, OCF.sub.2 --CHF--CF.sub.3, --C.sub.6 F.sub.13, --O--CF.sub.2 --CHF.sub.2
(h) Halogenorganosilanes of the type X.sub.3 Si(CH.sub.2).sub.m --R'
(i) Halogenorganosilanes of the type (R)X.sub.2 Si(CH.sub.2).sub.m --R'
(j) Halogenorganosilanes of the type (R).sub.2 X Si(CH.sub.2).sub.m --R'
(k) Silazanes of the type ##STR7## R=alkyl R'=alkyl, vinyl
(1) Cyclic polysiloxanes of the type D 3, D 4, D 5 in which D 3, D 4 and D 5 signify cyclic polysiloxanes with 3, 4 or 5 units of the type --O--Si(CH.sub.3).sub.2 --, e.g. octamethylcyclotetrasiloxane=D 4 ##STR8## (m) polysiloxanes or silicone oils of the type ##STR9## R=alkyl such as C.sub.n H.sub.2n+1 in which n=1 to 20, aryl such as phenyl- and substituted phenyl groups, (CH.sub.2).sub.n --NH.sub.2, H
Further subject matter of the invention is constituted by a method of producing the surface-modified, pyrogenically produced mixed oxides in accordance with the invention which is characterized in that two or more metal chlorides of the series SiCl.sub.4, AlCl.sub.3, TiCl.sub.4, ZrCl.sub.4, FeCl.sub.3, NbCl.sub.5, VOCl.sub.3, WOCl.sub.4, WCl.sub.6, SnCl.sub.4 and GeCl.sub.4 are evaporated [vaporized] together or separately, transferred together with an inert gas, e.g. nitrogen, into the mixing chamber of a known burner, mixed there with hydrogen, air and/or oxygen, the multi-component mixture burned in a reaction chamber, the solid mixed oxides separated thereafter from the gaseous reaction products and optionally freed in moist air from adhering hydrogen chloride and the pyrogenically produced mixed oxides placed in a suitable mixing container, the mixed oxides sprayed under intensive mixing optionally with water at first and then with the surface-modifying reagent or the mixture of several surface-modifying reagents, mixed again 15 to 30 minutes and subsequently tempered at a temperature of 100 to 400.degree. C. for a period of 1 to 6 hours.
The water used can be acidified with an acid, e.g. hydrochloric acid, from pH 7 to 1. The surface-modifying reagent used can be dissolved in a suitable solvent such as e.g. ethanol. The mixing and/or tempering can be carried out in an atmosphere of protective gas such as, for example, nitrogen.
Further subject matter of the invention constitutes a method of producing the surface-modified, pyrogenically produced mixed oxides which is characterized in that two or more metal chlorides from the series SiCl.sub.4, AlCl.sub.3, TiCl.sub.4, ZrCl.sub.4, FeCl.sub.3, NbCl.sub.5, VOCl.sub.3, WOCl.sub.4, WCl.sub.6, SnCl.sub.4 and GeCl.sub.4 are evaporated [vaporized] together or separately, transferred together with an inert gas, e.g. nitrogen, into the mixing chamber of a known burner, mixed there with hydrogen, air and/or oxygen. The multi-component mixture is burned in a reaction chamber, the solid mixed oxides separated thereafter from the gaseous reaction products and optionally freed in moist air from adhering hydrogen chloride and mixed as homogeneously as possible with organohalogen silanes with the exclusion of oxygen, the mixture heated together with slight amounts of water vapor and optionally together with an inert gas in a continuous process [continuous-current process which takes place in a continuous manner] in an upright treatment space designed as a tubular oven to temperatures of 200 to 800.degree. C., preferably 400 to 600.degree. C., the solid and gaseous reaction products separated from each other and the solid products optionally deacidified and dried.
Further subject matter of the invention constitutes the use of the surface-modified, pyrogenically produced mixed oxides in accordance with the invention as